Neutral ionic liquids with catalytic amount of acid have been employed for coumarin synthesis via Pechmann condensation of phenols and ethyl acetoacetate under ambient conditions. The reaction was also successfully carried out at high temperature in 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid, without the use of any acid catalyst. The possibility of Bronsted acidic ionic liquids catalysing this reaction has also been investigated. Ionic liquids were recycled efficiently. (c) 2005 Elsevier B.V. All rights reserved.